US3573292A - Novel oxygen complexes and process for the production thereof - Google Patents
Novel oxygen complexes and process for the production thereof Download PDFInfo
- Publication number
- US3573292A US3573292A US690764A US3573292DA US3573292A US 3573292 A US3573292 A US 3573292A US 690764 A US690764 A US 690764A US 3573292D A US3573292D A US 3573292DA US 3573292 A US3573292 A US 3573292A
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- US
- United States
- Prior art keywords
- oxygen
- bis
- complexes
- nickel
- group
- Prior art date
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- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 title description 13
- 150000002926 oxygen Chemical class 0.000 title description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 abstract description 27
- 239000001301 oxygen Substances 0.000 abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052751 metal Inorganic materials 0.000 abstract description 25
- 239000002184 metal Substances 0.000 abstract description 25
- 150000002739 metals Chemical class 0.000 abstract description 17
- 150000001875 compounds Chemical class 0.000 abstract description 16
- 230000000737 periodic effect Effects 0.000 abstract description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- UYLRKRLDQUXYKB-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UYLRKRLDQUXYKB-UHFFFAOYSA-N 0.000 description 18
- 229910052759 nickel Inorganic materials 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- FPZZZGJWXOHLDJ-UHFFFAOYSA-N trihexylphosphane Chemical compound CCCCCCP(CCCCCC)CCCCCC FPZZZGJWXOHLDJ-UHFFFAOYSA-N 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 4
- -1 cyclodoecyne Natural products 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- GEQBPMNDDHGGPJ-UHFFFAOYSA-N tri(piperidin-1-yl)phosphane Chemical compound C1CCCCN1P(N1CCCCC1)N1CCCCC1 GEQBPMNDDHGGPJ-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 3
- 229910000074 antimony hydride Inorganic materials 0.000 description 3
- 229940117916 cinnamic aldehyde Drugs 0.000 description 3
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- FDIOSTIIZGWENY-UHFFFAOYSA-N n-[bis(diethylamino)phosphanyl]-n-ethylethanamine Chemical compound CCN(CC)P(N(CC)CC)N(CC)CC FDIOSTIIZGWENY-UHFFFAOYSA-N 0.000 description 3
- KFBKRCXOTTUAFS-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KFBKRCXOTTUAFS-UHFFFAOYSA-N 0.000 description 3
- 229910052762 osmium Inorganic materials 0.000 description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical compound [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 3
- WWVNWQJKWKSDQM-UHFFFAOYSA-N triethylarsane Chemical compound CC[As](CC)CC WWVNWQJKWKSDQM-UHFFFAOYSA-N 0.000 description 3
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 3
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 3
- CYABZYIVQJYRDT-UHFFFAOYSA-N trimorpholin-4-ylphosphane Chemical compound C1COCCN1P(N1CCOCC1)N1CCOCC1 CYABZYIVQJYRDT-UHFFFAOYSA-N 0.000 description 3
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical compound C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 description 3
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229940095076 benzaldehyde Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 208000001848 dysentery Diseases 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002527 isonitriles Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- QJPQVXSHYBGQGM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJPQVXSHYBGQGM-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 235000021286 stilbenes Nutrition 0.000 description 2
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WHSDAOPXSDERMO-UHFFFAOYSA-N C1C[Ni]1.C1CCC(CC1)P(C1CCCCC1)C1CCCCC1.C1CCC(CC1)P(C1CCCCC1)C1CCCCC1 Chemical group C1C[Ni]1.C1CCC(CC1)P(C1CCCCC1)C1CCCCC1.C1CCC(CC1)P(C1CCCCC1)C1CCCCC1 WHSDAOPXSDERMO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021078 Pd—O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- SYKXNRFLNZUGAJ-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SYKXNRFLNZUGAJ-UHFFFAOYSA-N 0.000 description 1
- XAKYZBMFCZISAU-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XAKYZBMFCZISAU-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- WSWCOQWTEOXDQX-MQQKCMAXSA-N sorbic acid group Chemical class C(\C=C\C=C\C)(=O)O WSWCOQWTEOXDQX-MQQKCMAXSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
- C07F15/0093—Platinum compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
Definitions
- This invention relates to novel oxygen complexes and a process for the production thereof.
- the process according to the invention comprises reacting complexes consisting of zero-valent metals of the VIIIth Sub-group and electron donors with molecular oxygen.
- the complexes prepared in accordance with the invention are novel compounds.
- tetrakis(triphenyl-phosphine)nickel(O) in suspension reacts in accordance with the invention with molecular oxygen at as low as 80 C.
- molecular oxygen at as low as 80 C.
- two triphenyl phosphine molecules are displaced from the nickel atom and a complex in which two molecules of triphenyl phosphine and one molecule of oxygen are bonded to nickel (O) is obtained according to the equation:
- This product being capable of being isolated.
- This compound is stable up to about 35 C. Above this temperature, it decomposes spontaneously with transfer of the oxygen activated by complex formation to the triphenyl phosphine molecules which are present at the same time.
- the reaction product obtained is triphenyl phosphine oxide in addition to highly active nickel.
- Suitable electron 3,573,292 Patented Mar. 30, 1971 donors for complexing with the transition metals mentioned above and to be bonded in zero-valent state include compounds which have hetero atoms with free electron pairs and these compounds together with compounds which have multiple bonds with 1r-electron systems.
- the compounds with hetero atoms which are chiefly used include alkyl, aralkyl, cycloalkyl and aryl compounds of the elements of main group V, i.e. of nitrogen, phosphorous, arsenic and antimony and amides of phosphorous acid, examples being triphenyl phosphine, tricyclohexyl phosphine, triisopropyl phosphine, triethyl phosphine, phosphorous acid tridiethylamide, phosphorous acid trimorpholide, triphenyl arsine, triphenyl arsenite triethyl arsine, triphenyl stibine, tripropyl stibine.
- Suitable compounds with 1r-electron systems include those which contain CC, CO, CN multiple bonds and the combination thereof to conjugated multiple bonds, and derivatives thereof, examples being ethylene, cyclooctadi-1,5-ene, cyclododecatri-1,5,9-ene, phenyl acetylene, tolane, stilbene, cyclodoecyne, benzaldehyde, acrolein, cinnamic aldehyde, acrylonitrile, acrylic acid esters, sorb-' ic acid esters, butadiene carboxylic acid esters, maleic anhydride, etc.
- the zero-valent metals are then combined in complexes in complexes in which both electron donors of the group first mentioned above and those of the second group are bonded.
- Zero-valent metal complexes with various electron donors include cyclooctadiene-nickel-(O')-'bis- (triphenyl phosphine), bis triphenylphosphine nickel- (O) ethylene, bis(triphenylphosphine)nickel(O)stilbene, bis(triphenyl phosphine)nickel(O)tolane, bis(tricyclohexyl phosphine)nickel(O)ethylene, bis(tripiperidinophosphine)nickel(O)ethylene, bis(triphenyl phosphine) palladium(0)cyclooctadiene, bis(tricyclohexyl phosphine)platinum(0)ethy1ene and bis(triphenyl phosphine) nickel(O)butadiene.
- triphenyl phosphine bis triphenylphosphine nickel- (O) ethylene
- the process according to the invention may be carried out in the presence and in the absence of solvents, but is preferably carried out in the presence of a solvent.
- Suitable solvents are those which neither attack the transition metal complexes to be used nor are themselves attacked by activated oxygen.
- suitable solvents include aliphatic, cycloaliphatic and aromatic hydrocarbons, ethers, esters such as hexane, cyclohexane, benzene, mixtures of saturated hydrocarbons (B.P. 60-200 C.), tetrahydrofuran, dioxane, diethyl ether. Mixtures of these solvents may also be used.
- the process according to the invention may be carried out at temperatures of from 100 to C., especially from to +50" C.
- novel complexes of zero-valent metals of Subgroup VIII of the Periodic Table which contain oxygen and electron donors as the only ligands are useful compounds in many respects.
- the complexes mentioned above are converted into oxygen compounds of the donors bonded to the metal, i.e. the oxygen of the complex is trans ferred to the other ligand, which is the electron donor.
- the oxygen of the complex is trans ferred to the other ligand, which is the electron donor.
- decomposition of bis(triphenylphosphine) nickel(O).O gives nearly pure triphenylphosphinc-oxide.
- an excess of electron donor may be oxidized catalytically on the metal.
- electron donors compounds having CN-multiple bonds like isonitriles it is possible to transfer oxygen catalyti- 3 cally by the complexes mentioned above. as catalysts to said electron donors, converting said electron donors into oxygen-containing compounds. Isonitriles are so converted into isocyanates, which are widely used in many fields, preferably in the production of plastics, foams.
- the new complexes many be used as starting materials for the preparation of finely-divided, high active metals of Sub-group VIII of the Periodic Table, which metals, preferably Pd, Pt and Ni, are well known catalysts for many purposes, because decomposition of the complexes gives metals of said complexes in a highlyactive form.
- EXAMPLE 1 35 grams of tetrakis(triphenyl phosphine)nickel in 350 g. of ether take up 1 g. of oxygen at -7 8 C. Thereby, the red-brown tetrakis(triphenyl phosphine)nickel is converted into the yellow bis(triphenylphosphine)nickel (O)oxygen complex which is freed from concomitantly formed triphenyl phosphine by extraction with cold ether at 78 C. If the pure compound which is suspended in ether is thereafter allowed to reach a temperature above 35 C., decomposition occurs while the color turns brown. The elemental nickel may be removed from the resultant mixture by means of dilute hydrochloric acid. When evaporated, the ether solution leaves behind 17 grams of triphenylphosphine oxide, i.e. substantially 100% of the triphenyl phosphine bonded to the oxygen complex have been oxidized.
- EXAMPLE 2 The oxygen complex of platinum is prepared, for example, by dissolving 5 g. of tetrakis(triphenylphosphine) platinum in 150 g. benzene and introducing oxygen at 20 C. until the solution is saturated, which takes about 1 hour with the quantities mentioned above.
- EXAMPLE 3 The palladium-oxygen complex isprepared, for example, by dissolving 11.9 g. of tetrakis(triphenylphosphine) palladium() in 150 g. of benzene and introducing oxygen at 0 C. Within 15 minutes, 0.33 g. of 0 are taken up. After filtration and washing with benzene, 6.0 g. 88% of the theory of bis(triphenyl phosphine) palladium(0) -O are obtained.
- Bis (triphenyl phosphine)nickel(0) -0 may also be prepared when starting from bis(triphenylphosphine)nickel (O)tolane. A suspension of 15.56 g. of this complex in 100 g. of ether is prepared and treated with oxygen at -78 C. (take-up, 0.64 g.). The product is purified as described in Example 1. The yield is substantially quantitative.
- a process for the production of novel complexes of zero-valent metals of Subgroup VIII of the Periodic Table, oxygen, and two Group Va electron donor molecules which comprises reacting complexes consisting of zero-valent metals of Sub-group VIII and electron donors selected from the group consisting of two Group Va electron donor ligands and one multiple bonded carbon atom-containing electron donor ligand containing bondable II electrons or four Group Va electron donor ligands with molecular oxygen at 100 to C.
- Group VIII metal is at least one member selected from the group consisting of nickel, palladium and platinum.
- Process according to claim 1 carried out in a solvent, which solvent is at least one member selected from the group consisting of aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons, ethers and esters.
- said multiple bonded carbon atom containing electron donor is at least one member selected from the group consisting of ethylene, cyclooctadi 1,5-ene, cyclododecatri 1,5-9-ene, phenyl acetylene, tolane, stilbene cyclododecyne benz aldehyde, acrolein, cinnamic aldehyde, acrylonitrile, acrylic acid esters, sorbic acid esters, butadiene carboxylic acid esters, and maleic anhydride.
- a process as claimed in claim 1 wherein said Group Va electron donors are selected from the group consisting of triphenylphosphine, tricyclohexylphosphine, triisopropylphosphine, triethylphosphine, phosphorous acid tri(diethyl amide), phosphorous acid trimorpholide, triphenyl arsine, triethyl arsine triphenyl stibine and tripropyl stibine.
- said metal is at least one member selected from the group consisting of nickel, palladium and platinum.
- said metal is at least one member selected from the group consisting of iron, cobalt, ruthenium, rhodium, osmium and iridium.
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Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEST026261 | 1966-12-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3573292A true US3573292A (en) | 1971-03-30 |
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ID=7460920
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US690764A Expired - Lifetime US3573292A (en) | 1966-12-17 | 1967-12-15 | Novel oxygen complexes and process for the production thereof |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3573292A (ja) |
| BE (1) | BE705852A (ja) |
| CH (1) | CH489535A (ja) |
| GB (1) | GB1196776A (ja) |
| NL (1) | NL6714637A (ja) |
| SE (1) | SE361176B (ja) |
| YU (1) | YU32783B (ja) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3711274A (en) * | 1969-05-19 | 1973-01-16 | Montedison Spa | Process for preparing finely particled nickel powder |
| US3760000A (en) * | 1971-03-15 | 1973-09-18 | Procter & Gamble | Preparation of phosphine oxides by catalytic oxidation of tertiary phosphines |
| US3891684A (en) * | 1971-11-04 | 1975-06-24 | Exxon Research Engineering Co | Preparation of organometallic complexes |
| WO1981003494A1 (en) * | 1980-06-06 | 1981-12-10 | W Hill | Manganese compounds and sorption of gases using manganese compounds |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3962250A (en) * | 1969-12-30 | 1976-06-08 | Snam Progetti S.P.A. | Oxidation products of cobalt complexes, process for obtaining same and insertion process |
-
1967
- 1967-10-17 SE SE14201/67A patent/SE361176B/xx unknown
- 1967-10-19 GB GB47568/67A patent/GB1196776A/en not_active Expired
- 1967-10-24 CH CH1493467A patent/CH489535A/de not_active IP Right Cessation
- 1967-10-27 NL NL6714637A patent/NL6714637A/xx unknown
- 1967-10-27 YU YU2096/67A patent/YU32783B/xx unknown
- 1967-10-30 BE BE705852D patent/BE705852A/xx unknown
- 1967-12-15 US US690764A patent/US3573292A/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3711274A (en) * | 1969-05-19 | 1973-01-16 | Montedison Spa | Process for preparing finely particled nickel powder |
| US3760000A (en) * | 1971-03-15 | 1973-09-18 | Procter & Gamble | Preparation of phosphine oxides by catalytic oxidation of tertiary phosphines |
| US3891684A (en) * | 1971-11-04 | 1975-06-24 | Exxon Research Engineering Co | Preparation of organometallic complexes |
| WO1981003494A1 (en) * | 1980-06-06 | 1981-12-10 | W Hill | Manganese compounds and sorption of gases using manganese compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| YU32783B (en) | 1975-08-31 |
| CH489535A (de) | 1970-04-30 |
| BE705852A (ja) | 1968-04-30 |
| GB1196776A (en) | 1970-07-01 |
| DE1593565B2 (de) | 1973-01-18 |
| DE1593565A1 (de) | 1970-07-23 |
| NL6714637A (ja) | 1968-06-18 |
| YU209667A (en) | 1975-02-28 |
| SE361176B (ja) | 1973-10-22 |
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